Pyrimidine derivatives, their production and use

ABSTRACT

A novel herbicidal pyrimidine derivative represented by the formula &lt;IMAGE&gt; (I)  wherein each of R1, R2, R3, R4, Y1, Y2, Y3, X and Z are as defined herein.

This is a division of application Ser. No. 602,689, filed Oct. 24, 1990, now U.S. Pat. No. 5,125,957.

The present invention relates to a novel pyrimidine derivative, a method for producing the same, there use as herbicides and an intermediate of the same.

European Patent Application No. 0233 406A1, 0249 708A1, 0249 707A1, etc. disclose the pyrimidine derivatives can be used as an active ingredient for herbicides.

However, these compounds are not always said to be satisfactory because they are insufficient in herbicidal activity.

On the other hand, a large number of herbicides for crop lands or non-crop lands are now in use. However, there are many kinds of weed to be controlled and generation of the weeds extends over a long period of time, so that development of herbicides having a higher herbicidal effect and a broader herbicidal spectrum is being desired. Further, in recent years, no-till cultivation is carried out for the purposes of saving in labor, extension of cultivation period, prevention of soil running-off, etc. Because of this, it is being much desired to develop herbicides having both a high post-emergence herbicidal activity against weeds and a pre-emergence herbicidal activity excellent in residual effect, and besides having excellent selectivity of crops when crops are cultivated after application of herbicides.

In view of the situation like this, the present inventors have extensively studied, and as a result, have found that a pyrimidine derivative represented by the following formula (I) is a compound having excellent herbicidal activity, having few foregoing defects and some of them, having excellent selectivity between crops and weeds. That is the said pyrimidine derivative is a compound which can control weeds widely generated in crop lands or non-crop lands at low dosage rate, has a broad herbicidal spectrum and also can safely be used for no-till cultivation. The present invention is based on this finding.

The present invention provides a pyrimidine derivative represented by the formula (I) [hereinafter referred to as present compounds (s)], a method for producing the same, their use as herbicides and an intermediate of the same: ##STR2## wherein each of R¹ and R², which may be the same or different, represents a hydrogen atom, a C₁ -C₆ alkyl group, a C₃ -C₆ alkenyl group, a C₃ -C₆ alkynyl group, a halo C₁ -C₆ alkyl group, a C₁ -C₆ alkoxy C₁ -C₆ alkyl group, a C₃ -C₆ alkenyloxy C₁ -C₆ alkyl group, a C₃ -C₆ alkynyloxy C₁ -C₆ alkyl group, a C₁ -C₆ alkoxycarbonyl C₁ -C₆ alkyl group a C₃ -C₆ alkenyloxycarbonyl C₁ -C₆ alkyl group, a C₃ -C₆ alkynyloxycarbonyl C₁ -C₆ alkyl group, a cyano C₁ -C₆ alkyl group, a group represented by the formula ##STR3## (in which each of R⁵ and R⁶, which may be the same or different, represents a hydrogen atom, a C₁ -C₆ alkyl group, a C₃ -C₆ alkenyl group or a C₃ -C₆ alkynyl group, and n represents an integer of 1, 2, 3, or 4), a group represented by the formula, ##STR4## (in which n is as defined above, R⁷ represents a C₁ -C₆ alkyl group, a C₃ -C₆ alkenyl group or a C₃ -C₆ alkynyl group, and m represents an integer of 0, 1 or 2), a cyclo C₃ -C₈ alkyl group, or an optionally substituted phenyl group, an optionally substituted benzyl group, or R¹ and R², bonded together at their ends, form an optionally substituted C₄ -C₇ alkylene group or an optionally substituted C₃ -C₆ alkylene group containing hereto atom; the hereto atom in R¹ and R² means a nitrogen atom, an oxygen atom or a sulfur atom; each of R³ and R⁴, which may be the same or different, represents a C₁ -C₆ alkyl group, a C₁ -C₄ alkoxy group, a halo C₁ -C₆ alkoxy group or a halogen atom; X represents an oxygen atom or a sulfur atom; Z represents N or CY⁴ ; each of Y¹, Y², Y³, which may be the same or different, represents a hydrogen atom, a halogen atom, a C₁ -C₆ alkyl group, or a C₁ -C₆ alkoxy group; and Y⁴ represents a hydrogen atom, a hydroxyl group, a mercapto group, a nitro group, a halogen atom, a C₁ -C₆ alkyl group, a C₂ -C₆ alkenyl group, a C₂ -C₆ alkenyl group, a C₁ -C₆ alkoxy group, a C₃ -C₆ alkenyloxy group, & C₃ -C₆ alkynyloxy group, a halo C₁ -C₆ alkyl group, a halo C₂ -C₆ alkenyl group, a halo C₂ -C₆ alkynyl group, a halo C₁ -C₆ alkoxy group, a halo C₃ -C₆ alkenyloxy group, a halo C₃ -C₆ alkynyloxy group, a C₁ -C₆ alkoxy C₁ -C₆ alkyl group, a C₃ -C₆ alkenyloxy C₁ -C₆ alkyl group, a C₃ -C₆ alkynyloxy C₁ -C₆ alkyl group, a cyano group, a formyl group, a carboxyl group, a C₁ -C₆ alkoxycarbonyl group, a C₃ -C₆ alkenyloxycarbonyl group, a C₃ -C₆ alkynyloxycarbonyl group; an optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted phenylthio group, an optionally substituted benzyloxy group, an optionally substituted benzylthio group, a group represented by the formula, ##STR5## (in which R⁵ and R⁶ are as defined above), a group represented by the formula, ##STR6## (in which R⁵ and R⁶ are as defined above). ##STR7## (in which R⁷ and m are as defined above), a group represented by the formula, ##STR8## (in which R⁷ and X are as defined above), or a group represented by the formula ##STR9## (in which R⁷, m and n are as defined above), each optionally substituted group in the above being substituted with a C₁ -C₆ alkyl group, a C₁ -C₆ alkoxy group, a halo C₁ -C₆ alkyl group, a C₁ -C₆ alkoxycarbonyl group or a halogen atom. In the compound of the formula (I), the substituents R³ and R⁴, which may be the same or different, are preferably a C₁ -C₄ alkoxy group, and more preferably, both of them are a methoxy group. X is preferably an oxygen atom. Z is preferably N or CY⁵ (in which Y⁵ represents a hydrogen atom, a halo C₁ -C₆ alkyl group, or a halogen atom. More preferably Z is CY⁵ and Y⁵ is a halo C₁ -C₄ alkyl group or a halogen atom, and more preferably Y⁵ is a halogen atom. Y¹, Y² and Y³ are preferably a hydrogen atom or a fluorine atom.

Specific examples of the pyrimidine derivative of the present invention include

4,6-dimethoxy-2-{2-(N,N-dimethylaminoxycarbon)phenoxy}pyrimidine,

4,6-dimethoxy-2-{3-chloro-2-(N,N-dimethylaminooxycarbonyl)phenoxy}pyrimidine,

4,6-dimethoxy-2-{3-fluoro-2-(N,N-dimethylaminooxycarbonyl)phenoxy}pyrimidine,

3-(4,6-dimethoxypyrimidin-2-yl)oxy-2-(N,N-dimethylaminooxycarbonyl)pyridine

4,6-dimethoxyl-2-{3-trifluoromethyl-2-(N,N-dimethylaminooxycarbonyl)phenoxy}pyrimidine,

4,6-dimethoxy-2-{3-chloro-2-(1-piperidyloxycarbonyl)phenoxy}pirimidine,

4,6-dimethoxy-2-{3-chloro-2-(N-tert-butylaminooxycarbonyl)phenoxy}pyrimidine.

A method for producing the present compound is as follows.

The present compound (I) can be produced by reacting a phenol derivative represented by the formula (II), ##STR10## [wherein R¹, R² X, Y¹, Y², Y³ and Z are as defined above], with a pyrimidine derivative represented by the formula (III), ##STR11## [wherein R³ and R⁴ are each as defined above] and W represents a halogen atom or a group represented by the formula, ##STR12## (in which R⁸ represents a C₁ -C₆ alkyl group or an benzyl group which being optionally substituted with C₁ -C₆ alkyl group C₁ -C₆ alkoxy group, a halogen atom or a nitro group, and m represents an integer of 0, 1 or 2).

This reaction is usually carried out with or without a solvent in the presence of a base. The reaction temperature ranges from room temperature to the boiling point of the solvent, and the reaction time ranges from 10 minutes to 24 hours. Referring to the amounts of the reagents used for this reaction, the amount of the pyrimidine derivative (III) is 1.0 to 1.5 equivalents based on 1 equivalent of the phenol derivative (II), and that of the base is 1.0 to 5.0 equivalents based on the same. The solvent includes aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene xylene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones (e.g. acetone, methylethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), alocohls (e.g. methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol, glycerin), esters (e.g. ethyl formate, ethylacetate, butyl acetate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g. formamide, N,N-dimethylformamide, acetamide), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane), liquid ammonia, water and mixtures thereof.

The base includes organic bases (e.g. pyridine, triethylamine, N,N-diethylaniline), inorganic bases (e.g. sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride), alkali metal alkoxides (e.g. sodium methoxide, sodium ethoxide), etc.

After completion of the reaction, the reaction solution is after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to chromatography, distillation, recrystallization, etc. Thus, the desired present compound can be obtained.

The pyrimidine derivative represented by the formula (III) can be produced according to Japanese Patent Application Kokai No. 63-23870, J. Org. Chem., 26, 792 (1961), etc.

The present compound can also be produced by reacting [reaction (i)] a pyrimidine derivative represented by the formula (IV), ##STR13## [wherein R³, R⁴, X, Y¹, Y², Y³ and Z are as defined above], with an acid-halogenating agent or an active esterifying agent, and subsequently reacting [reaction (ii)] the resulting reaction product with a hydroxylamine derivative represented by the formula (V), ##STR14## (wherein R¹ and R² are as defined above).

In the above reaction (i), the acid-halogenating agent includes thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosgene, oxalic acid dichloride, etc. The active esterifying agent include N,N'-disubstituted carbodimides such as N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, etc.; arylsulfonyl chlorides such as 2,4,6-trimethylbenzenesulfonyl chloride, 2,4,6-triisopropylbenzenesulfonyl chloride, etc.; N,N'-carbonyldiimidazole; diphenylphosphorylazide; N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline; N-ethyl-2'-hydroxybenzisoxazolium trifluoroborate; N-ethyl-5-phenylisoxazolium-3'-sulfonate; etc.

By this reaction, a pyrimidine derivative represented by the formula (VI); ##STR15## wherein R³, R⁴, X, Y¹, Y², Y³ and Z are as defined above, is produced in the reaction system.

In the above formula (VI), a substituent W² represents a halogen atom when the acid-halogenating agent was used; W² represents an N,N'-disubstituted-2-isoureide group when N,N'-disubstituted carbodiimide was used as the active esterifying agent; W² represents an arylsulfonyloxy group when arylsulfonyl chloride was used as said agent; W² represents an imidazolyl group when N,N'-carbonyldiimidazole was used as said agent; W² represents an azide group when diphenylphosphorylazide was used as said agent; W² represents a ethoxycarbonyloxy group when N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline was used as said agent; W² represents a 3-(N-ethylaminocarbonyl)-2-hydroxyphenoxy group when N-ethyl- 2'-hydroxybenzisoxazolium trifluoroborate was used as said agent; and W² represents a group ##STR16## when N-ethyl-5-phenylisoxazolium-3'-sulfonate was used as said agent.

In the reaction system, W² can also take a form of acid anhydride represented by the formula, ##STR17## (wherein R³, R⁴, X, Y¹, Y², Y³ and Z are as defined above.)

The amount of the a foregoing acid-halogenating agent or active esterifying agent used is usually 1 to 10 equivalents based on 1 equivalent of the pyrimidine derivative represented by the formula (IV).

The amount of hydroxylamine derivative of the formula (V) used is usually 1 to 5 equivalents based on 1 equivalent of the pyrimidine derivative represented by the formula (IV).

The reactions (i) and (ii) can also be carried out, if necessary, in the presence of a base. Such a base includes organic bases (e.g. 1-methylimidazole, 3-nitro-1H-1,2,4-triazole, 1H-tetrazole, 1H-1,2,4-triazole, imidazole, pyridine, triethylamine) and inorganic bases (e.g. potassium carbonate). The amount of the base used is 1 to 20 equivalents based on 1 equivalent of the pyrimidine derivative represented by the formula (IV).

The reactions (i) and (ii) are usually carried out in the presence of an inert solvent. Such a solvent includes aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chloroborm, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), esters (e.g. ethylformate, ethyl acetate, butyl acetate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g. N,N-dimethylformamide), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane) and mixtures thereof.

Generally, the reaction temperature ranges from 0° C. to the boiling point of the solvent in any of the reactions (i) and (ii). The reaction time ranges from 1 to 24 hours for each reaction, and from about 1 to about 48 hours through the reactions (i) and (ii).

After completion of the reaction, the reaction solution is after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to chromatography, distillation, recrystallization, etc. Thus, the desired present compound can be obtained.

The pyrimidine derivative represented by the formula (IV) can be produced according to Japanese Patent Application Kokai No. 62-174059, etc.

Table 1 illustrates examples of the compound (I) which can be produced by the above procedures.

                                      TABLE 1                                      __________________________________________________________________________      ##STR18##                                                                     R.sup.1      R.sup.2      Y.sup.1                                                                            Y.sup.2                                                                            Y.sup.3                                                                            Z            X R.sup.3                                                                             R.sup.4              __________________________________________________________________________     H            H            H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            H            H            H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            H            H            H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            H            H            H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            H            CH.sub.3     H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            H            CH.sub.3     H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            H            CH.sub.3     H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            H            CH.sub.3     H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CH           S OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CH           O Cl   OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CH           O CH.sub.3                                                                            CH.sub.3             CH.sub.3     CH.sub.3     CH.sub.3                                                                           H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   CH.sub.3                                                                           H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   CH.sub.3                                                                           CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCH.sub.3    O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CC.sub.2 H.sub.5                                                                            O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     OCH.sub.3                                                                          H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   OCH.sub.3                                                                          H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   OCH.sub.3                                                                          CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COCH.sub.3   O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     F   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   F   H   CH           O OCH.sub.3                                                                           OCH.sub. 3           CH.sub.3     CH.sub.3     H   H   F   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CF           O OCH.sub.3                                                                           Cl                   CH.sub.3     CH.sub.3     H   H   F   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     F   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     F   H   F   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     Cl  H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   Cl  H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   Cl  CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   F   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CBr          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   Cl           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COH          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CSH          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CNO.sub.2    O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCHCH.sub.2  O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCCH         O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COC.sub.2 H.sub.5                                                                           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 CHCH.sub.2                                                                       O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 CCH                                                                              O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 C(Cl)CH.sub.2                                                                     O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCCI         O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COCF.sub.3   O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 CHCHCl                                                                           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 C CI                                                                             O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 OCH.sub.3                                                                         O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 OCH.sub.2 CHCH.sub.2                                                              O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 OCH.sub.2 CCH                                                                     O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCN          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCHO         O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCOOH        O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCOOCH.sub.3 O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCOOCH.sub.2 CHCH.sub.2                                                                     O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCOOCH.sub.2 CCH                                                                            O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CC.sub.6 H.sub.5                                                                            O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COC.sub.6 H.sub.5                                                                           O OCH.sub.                                                                            OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CSC.sub.6 H.sub.5                                                                           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 C.sub.6 H.sub.5                                                                  O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CSCH.sub.2 C.sub.6 H.sub.5                                                                  O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CNH.sub.2    O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CN(CH.sub.3).sub.2                                                                          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CN(CH.sub.2 CHCH.sub.2).sub.2                                                               O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CN(CH.sub.2 CCH).sub.2                                                                      O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCONH.sub.2  O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCON(C.sub.2 H.sub.5).sub.2                                                                 O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCON(CH.sub.2 CHCH.sub.2).sub.2                                                             O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCON(CH.sub.2 C CH).sub.2                                                                   O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CSCH.sub.3   O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CSOC.sub.2 H.sub.5                                                                          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CSO.sub.2 C.sub.3 H.sub.7 (n)                                                               O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CSCH.sub.2 CHCH.sub.2                                                                       O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CSCH.sub.2 CCH                                                                              O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 CH.sub.2 SCH.sub.3                                                                O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   C(CH.sub.2).sub.3 SOCH.sub.3                                                                O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 SO.sub.2 CH.sub.3                                                                 O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.3     H   H   H   CH           O OCHF.sub.2                                                                          OCHF.sub.2           CH.sub.3     CH.sub.3     H   H   H   N            O OCHF.sub.2                                                                          OCHF.sub.2           CH.sub.3     CH.sub.3     H   H   H   CF           O OCHF.sub.2                                                                          OCHF.sub.2           CH.sub.3     CH.sub.3     H   H   H   CCl          O OCHF.sub.2                                                                          OCHF.sub.2           CH.sub.3     CH.sub.3     H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     C.sub.2 H.sub.5                                                                             H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CHCH.sub.2                                                                         CH.sub.2 CHCH.sub.2                                                                         H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CHCH.sub.2                                                                         CH.sub.2 CHCH.sub.2                                                                         H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CCH CH.sub.2 CCH H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CCH CH.sub.2 CCH H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 Cl                                                                        CH.sub.2 CH.sub.2 Cl                                                                        H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 Cl                                                                        CH.sub.2 CH.sub.2 Cl                                                                        H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.2 CH.sub.2 OCH.sub.3                                                                 H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.2 CH.sub.2 OCH.sub.3                                                                 H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR19##                                                                                   ##STR20##   H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR21##                                                                                   ##STR22##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR23##                                                                                   ##STR24##   H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR25##                                                                                   ##STR26##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 COOCH.sub.3                                                                        CH.sub.2 COOCH.sub.3                                                                        H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 COOCH.sub.3                                                                        CH.sub.2 COOCH.sub.3                                                                        H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.2 COOCH.sub.3                                                                        H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.2 COOCH.sub.3                                                                        H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3                                                                                     ##STR27##   H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3                                                                                     ##STR28##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.2 CH.sub.2 COOCH.sub.3                                                               H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.2 CH.sub.2 COOCH.sub.3                                                               H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR29##                                                                                   ##STR30##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR31##                                                                                   ##STR32##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR33##                                                                                   ##STR34##   H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR35##                                                                                   ##STR36##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CN  CH.sub.2 CN  H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CN  CH.sub.2 CN  H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 CN                                                                        CH.sub.2 CH.sub.2 CN                                                                        H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 CN                                                                        CH.sub.2 CH.sub.2 CN                                                                        H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.2 CH.sub.2 CN                                                                        H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.2 CH.sub.2 CN                                                                        H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CONH.sub.2                                                                         CH.sub.2 CONH.sub.2                                                                         H   H   H   CF           O OCH.sub.                                                                            OCH.sub.3            CH.sub.2 CONH.sub.2                                                                         CH.sub.2 CONH.sub.2                                                                         H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CON(CH.sub.3).sub.2                                                                CH.sub.2 CON(CH.sub.3).sub.2                                                                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CON(CH.sub.3).sub.2                                                                CH.sub.2 CON(CH.sub.3).sub.2                                                                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR37##                                                                                   ##STR38##   H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR39##                                                                                   ##STR40##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR41##                                                                                   ##STR42##   H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR43##                                                                                   ##STR44##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.2 CH.sub.2 CONH.sub.2                                                                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     CH.sub.2 CH.sub.2 CONH.sub.2                                                                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 SCH.sub.3                                                                 CH.sub.2 CH.sub.2 SCH.sub.3                                                                 H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 SCH.sub.3                                                                 CH.sub.2 CH.sub.2 SCH.sub.3                                                                 H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 SOCH.sub.3                                                                CH.sub.2 CH.sub.2 SOCH.sub.3                                                                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 SOCH.sub.3                                                                CH.sub.2 CH.sub.2 SOCH.sub.3                                                                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                         CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                         H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                         CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                         H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            H            cyclohexyl   H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            H            cyclohexyl   H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            H            cyclohexyl   H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            H            cyclohexyl   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            H            cyclohexyl   H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3                          ##STR45##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            H                                                                                            ##STR46##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            H                                                                                            ##STR47##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3                                                                                     ##STR48##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3                                                                                     ##STR49##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3                                                                                     ##STR50##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR51##                                                                                   ##STR52##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR53##                                                                                   ##STR54##   H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3             ##STR55##                                                                                   ##STR56##   H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3             ##STR57##                                                                                   ##STR58##   H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR59##                                                                                   ##STR60##   H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR61##                                                                                   ##STR62##   H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3             ##STR63##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR64##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR65##                H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3             ##STR66##                H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3             ##STR67##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR68##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR69##                H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3             ##STR70##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR71##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR72##                H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3             ##STR73##                H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3             ##STR74##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR75##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR76##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR77##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR78##                H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3             ##STR79##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR80##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                                      H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                                      H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR81##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     C.sub.2 H.sub.5                                                                             H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     C.sub.2 H.sub.5                                                                             H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            CH.sub.3     C.sub.2 H.sub.5                                                                             H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3            C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3            C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                                      H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                                      H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3             ##STR82##                H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3             ##STR83##                H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                      H   H   H   CH           O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                      H   H   H   N            O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                      H   H   H   CCF.sub.3    O OCH.sub.3                                                                           OCH.sub.3             ##STR84##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR85##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR86##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR87##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR88##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR89##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR90##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR91##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3             ##STR92##                H   H   H   CF           O OCH.sub.3                                                                           OCH.sub.3             ##STR93##                H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                             H   H   H   CCl          O OCH.sub.3                                                                           OCH.sub.3            __________________________________________________________________________

In producing the present compounds, when the phenol derivative (a starting compound of compound (I)), represented by the formula (II) is other than those in which Y⁴ is a group, ##STR94## (in which R⁶ is as defined above) or a group, ##STR95## ps (in which R⁶ is as defined above), said phenol derivative can be produced by reacting an aromatic carboxylic acid halide derivative represented by the following formula (VIII) with the hydroxylamine derivative represented by the formula (V) in the presence of a dehydrohalogenating agent and then hydrolyzing the resulting compound with a base (e.g. sodium hydroxide, potassium hydroxide) or an acid (e.g. hydrochloric acid, sulfuric acid) to remove the group, wherein X, Y¹, Y² and Y³ are as defined above, W³ represents a halogen atom, R⁹ represents a C₁ -C₆ alkyl group, and Z represents CY⁴ ' wherein Y⁴ ' represents a hydrogen atom, a nitro group, a halogen atom, a C₁ -C₆ alkyl group, a C₂ -C₆ alkenyl group, a C₂ -C₆ alkynyl group, a C₁ -C₆ alkoxy group, a C₃ -C₆ alkenyloxy group, a C₃ -C₆ alkynyloxy group, a halo C₁ -C₆ alkyl group ,a halo C₂ -C₆ alkenyl group, a halo C₂ -C₆ alkynyl group, a halo C₁ -C₆ alkoxy group, a halo C₃ -C₆ alkenyloxy group, a halo C₃ -C₆ alkynyloxy group, a C₁ -C₆ alkoxy C₁ -C₆ alkyl group, a C₃ -C₆ alkenyloxy C₁ -C₆ alkyl group, a C₃ -C₆ alkyl group, a cyano group, a formyl group, a carboxyl group, a C₁ -C₆ alkoxycarbonyl group, a C₃ -C₆ alkenyloxycarbonyl group, a C₃ -C₆ alkynyloxycarbonyl group; a phenyl, phenoxy, phenylthio, benzyloxy or benzylthio group which being optionally substituted with a C₁ -C₆ alkyl group, a C₁ -C₆ alkoxy group, a halo C₁ -C₆ alkyl group, a C₁ -C₆ alkoxycarbonyl group or a halogen atom; and a group represented by the formula, ##STR96## (in which each of R⁵ ' and R⁶ ', which may be the same or different, represents a C₁ -C₆ alkyl group, a C₃ -C₆ alkenyl group or a C₃ -C₆ alkynyl group), a group represented by the formula ##STR97## (in which R⁵ ' and R⁶ ' are as defined above), a group represented by the formula, ##STR98## (in which R⁷ and m areas defined above), a group represented by the formula, ##STR99## (in which R⁷ and X areas defined above, a group represented by the formula ##STR100## (in which R⁷, m and n are as defined above), or a group represented by the formula, ##STR101## (in which R⁹ and X are as defined as defined above).

The dehydrohalogenating agent includes pyridine, triethylamine, N,N-diethylaniline, etc.

After completion of the reaction, the reaction solution is after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to the chromatography. distillation, recrystallization, etc. Thus, the phenol derivative (II) can be obtained.

The phenol derivative represented by the formula (II) can also be product by reacting [reaction (iii)] an aromatic carboxylic acid derivative represented by the formula (VIII), ##STR102## (wherein X, Y¹, Y², Y³ and Z are as defined above), with an acid-halogenating agent or an active esterifying agent, and subsequently reacting [reaction (iv)] the resulting reaction product with the hydroxylamine derivative represented by the formula (V).

The above reactions (iii) and (iv) are carried out according to the foregoing reactions (i) and (ii), respectively. The aromatic carboxylic acid halide derivative (VII) can be produced according to Beilstein H10/p. 86, EI10/p.43, EII10/p.55, EIII10/p.151, EIV10/p.169, etc.

The aromatic carboxylic acid derivative (VIII) can be produced according to J. Org. Chem., 27, 3551 (1962), Chem. Pharm. Bull., 31, 407 (1983), Yakugaku Zasashi, 99, 657 (1979), Chem. Pharm. Bull., 27, 1468 (1979), J. Med. Chem., 21, 1093 (1978), Yakugaku Zasshi, 92, 1386 (1972), Eur. J. Med. Chem-Chim. Ther., 21, 379 (1986), J. Chem. Soc., Perkin Trans. 1, 2069 (1979), J. Chem. Soc., Perkin Trans. 1, 2079 (1979), J. Chem. Soc., Chem. Commun., 1127 (1968), J. Med. Chem., 31, 1039, (1988), Indian J. Chem., 25B, 796 (1986), J. Am. Chem. Soc., 107, 4593 (1985), J. Org. Chem., 50, 718 (1985), J. Agric. Food Chem., 32, 747 (1984), J. Pharm. Pharmacol., 35, 718 (1983), J. Org. Chem., 48, 1935 (1983), J. Chem., Soc., Chem. commun., 1974, 362, etc.

The hydroxylamine derivative [V] can be produced according to Beilstein H/P.533, E II/P. 952, E III/p. 1713, E IV/p. 3299, Chem. Bar., 35, 703 (1902), Chem. Ber., 33, 3387 (1900), Chem. Ber., 34, 738 (1901), Chem. Ber., 62, 2458 (1929), J. Am. Chem. Soc., 76, 2984 (1954), J. Org. Chem., 25, 621 (1960), Chem. Ber., 56, 1856 (1923), Chem., Ber., 58, 2430 (1925), J. Org. Chem., 28, 265 (1963), Org. Synth. Coll. Vol. III, p. 668, Chem. Ber., 36, 2700 (1903), Chem. Ber., 42, 2306 (1909), J. Am. Chem. Soc., 83, 1374 (1961), Chem., Ber., 71, 2247 (1938), Chem. Ber., 41, 1936 (1908). Synth. Commun., 19, 3509 (1989), J. Org. Chem., 55, 1981 (1990), Synthesis, 1977, 856, Org. Synth. Coll. Vol. IV, p. 612.

Table 2 illustrates examples of the compound (II) which can be produced by the above procedures. Compound (I) and Compound (II) includes their stereo isomers having herbicidal activity.

                                      TABLE 2                                      __________________________________________________________________________      ##STR103##                                                                    R.sup.1      R.sup.2      Y.sup.1                                                                            Y.sup.2                                                                            Y.sup.3                                                                            Z            X                           __________________________________________________________________________     H            H            H   H   H   CH           O                           H            H            H   H   H   N            O                           H            H            H   H   H   CCl          O                           H            H            H   H   H   CF           O                           H            CH.sub.3     H   H   H   CH           O                           H            CH.sub.3     H   H   H   N            O                           H            CH.sub.3     H   H   H   CCl          O                           H            CH.sub.3     H   H   H   CF           O                           CH.sub.3     CH.sub.3     H   H   H   CH           O                           CH.sub.3     CH.sub.3     H   H   H   CH           S                           CH.sub.3     CH.sub.3     H   H   H   CH           O                           CH.sub.3     CH.sub.3     CH.sub.3                                                                           H   H   CH           O                           CH.sub.3     CH.sub.3     H   CH.sub.3                                                                           H   CH           O                           CH.sub.3     CH.sub.3     H   H   CH.sub.3                                                                           CH           O                           CH.sub.3     CH.sub.3     H   H   H   CCH.sub.3    O                           CH.sub.3     CH.sub.3     H   H   H   CC.sub.2 H.sub.5                                                                            O                           CH.sub.3     CH.sub.3     OCH.sub.3                                                                          H   H   CH           O                           CH.sub.3     CH.sub.3     H   OCH.sub.3                                                                          H   CH           O                           CH.sub.3     CH.sub.3     H   H   OCH.sub.3                                                                          CH           O                           CH.sub.3     CH.sub.3     H   H   H   COCH.sub.3   O                           CH.sub.3     CH.sub.3     F   H   H   CH           O                           CH.sub.3     CH.sub.3     H   F   H   CH           O                           CH.sub.3     CH.sub.3     H   H   F   CH           O                           CH.sub.3     CH.sub.3     H   H   H   CF           O                           CH.sub.3     CH.sub.3     H   H   F   CF           O                           CH.sub.3     CH.sub.3     F   H   H   CF           O                           CH.sub.3     CH.sub.3     F   H   F   CF           O                           CH.sub.3     CH.sub.3     Cl  H   H   CH           O                           CH.sub.3     CH.sub.3     H   Cl  H   CH           O                           CH.sub.3     CH.sub.3     H   H   Cl  CH           O                           CH.sub.3     CH.sub.3     H   H   H   CCl          O                           CH.sub.3     CH.sub.3     H   H   F   CCl          O                           CH.sub.3     CH.sub.3     H   H   H   CBr          O                           CH.sub.3     CH.sub.3     H   H   H   CI           O                           CH.sub.3     CH.sub.3     H   H   H   COH          O                           CH.sub.3     CH.sub.3     H   H   H   CSH          O                           CH.sub.3     CH.sub.3     H   H   H   CNO.sub.2    O                           CH.sub.3     CH.sub.3     H   H   H   CCHCH.sub.2  O                           CH.sub.3     CH.sub.3     H   H   H   CCCH         O                           CH.sub.3     CH.sub.3     H   H   H   COC.sub.2 H.sub.5                                                                           O                           CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 CHCH.sub.2                                                                       O                           CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 CCH                                                                              O                           CH.sub.3     CH.sub.3     H   H   H   CCF.sub.3    O                           CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 C(Cl)CH.sub.2                                                                     O                           CH.sub.3     CH.sub.3     H   H   H   CCCI         O                           CH.sub.3     CH.sub.3     H   H   H   COCF.sub.3   O                           CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 CHCHCl                                                                           O                           CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 CCI                                                                              O                           CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 OCH.sub.3                                                                         O                           CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 OCH.sub.2 CHCH.sub.2                                                              O                           CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 OCH.sub.2 CCH                                                                     O                           CH.sub.3     CH.sub.3     H   H   H   CCN          O                           CH.sub.3     CH.sub.3     H   H   H   CCHO         O                           CH.sub.3     CH.sub.3     H   H   H   CCOOH        O                           CH.sub.3     CH.sub.3     H   H   H   CCOOCH.sub.3 O                           CH.sub.3     CH.sub.3     H   H   H   CCOOCH.sub.2 CHCH.sub.2                                                                     O                           CH.sub.3     CH.sub.3     H   H   H   CCOOCH.sub.2 CCH                                                                            O                           CH.sub.3     CH.sub.3     H   H   H   CC.sub.6 H.sub.5                                                                            O                           CH.sub.3     CH.sub.3     H   H   H   COC.sub.6 H.sub.5                                                                           O                           CH.sub.3     CH.sub.3     H   H   H   CSC.sub.6 H.sub.5                                                                           O                           CH.sub.3     CH.sub.3     H   H   H   COCH.sub.2 C.sub.6 H.sub.5                                                                  O                           CH.sub.3     CH.sub.3     H   H   H   CSCH.sub.2 C.sub.6 H.sub.5                                                                  O                           CH.sub.3     CH.sub.3     H   H   H   CNH.sub.2    O                           CH.sub.3     CH.sub.3     H   H   H   CN(CH.sub.3).sub.2                                                                          O                           CH.sub.3     CH.sub.3     H   H   H   CN(CH.sub.2 CHCH.sub.2).sub.2                                                               O                           CH.sub.3     CH.sub.3     H   H   H   CN(CH.sub.2 C CH).sub.2                                                                     O                           CH.sub.3     CH.sub.3     H   H   H   CCONH.sub.2  O                           CH.sub.3     CH.sub.3     H   H   H   CCON(C.sub.2 H.sub.5).sub.2                                                                 O                           CH.sub.3     CH.sub.3     H   H   H   CCON(CH.sub.2 CHCH.sub.2).sub.2                                                             O                           CH.sub.3     CH.sub.3     H   H   H   CCON(CH.sub.2 CCH).sub.2                                                                    O                           CH.sub.3     CH.sub.3     H   H   H   CSCH.sub.3   O                           CH.sub.3     CH.sub.3     H   H   H   CSOC.sub.2 H.sub.5                                                                          O                           CH.sub.3     CH.sub.3     H   H   H   CSO.sub.2 C.sub.3 H.sub.7 (n)                                                               O                           CH.sub.3     CH.sub.3     H   H   H   CSCH.sub.2 CHCH.sub.2                                                                       O                           CH.sub.3     CH.sub.3     H   H   H   CSCH.sub.2 CCH                                                                              O                           CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 CH.sub.2 SCH.sub.3                                                                O                           CH.sub.3     CH.sub.3     H   H   H   C(CH.sub.2).sub.3 SOCH3                                                                     O                           CH.sub.3     CH.sub.3     H   H   H   CCH.sub.2 SO.sub.2 CH.sub.3                                                                 O                           CH.sub.3     CH.sub.3     H   H   H   N            O                           CH.sub.3     C.sub.2 H.sub.5                                                                             H   H   H   CF           O                           CH.sub.3     C.sub.2 H.sub.5                                                                             H   H   H   CCl          O                           C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   CF           O                           C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   CCl          O                           C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   CF           O                           C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   CCl          O                           H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   CH           O                           H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   N            O                           H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   CF           O                           H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   CCl          O                           H            C.sub.3 H.sub.7 (l)                                                                         H   H   H   CCF.sub.3    O                           H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   CH           O                           H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   N            O                           H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   CF           O                           H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   CCl          O                           H            C.sub.4 H.sub.9 (tert)                                                                      H   H   H   CCF.sub.3    O                           CH.sub.2 CHCH.sub.2                                                                         CH.sub.2 CHCH.sub.2                                                                         H   H   H   CF           O                           CH.sub.2 CHCH.sub.2                                                                         CH.sub.2 CHCH.sub.2                                                                         H   H   H   CCl          O                           CH.sub.2 CCH CH.sub.2 CCH H   H   H   CF           O                           CH.sub.2 CCH CH.sub.2 CCH H   H   H   CCl          O                           CH.sub.2 CH.sub.2 Cl                                                                        CH.sub.2 CH.sub.2 Cl                                                                        H   H   H   CF           O                           CH.sub.2 CH.sub.2 Cl                                                                        CH.sub.2 CH.sub.2 Cl                                                                        H   H   H   CCl          O                           CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.2 CH.sub.2 OCH.sub.3                                                                 H   H   H   CF           O                           CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.2 CH.sub.2 OCH.sub.3                                                                 H   H   H   CCl          O                            ##STR104##                                                                                  ##STR105##  H   H   H   CF           O                            ##STR106##                                                                                  ##STR107##  H   H   H   CCl          O                            ##STR108##                                                                                  ##STR109##  H   H   H   CF           O                            ##STR110##                                                                                  ##STR111##  H   H   H   CCl          O                           CH.sub.2 COOCH.sub.3                                                                        CH.sub.2 COOCH.sub.3                                                                        H   H   H   CF           O                           CH.sub.2 COOCH.sub.3                                                                        CH.sub.2 COOCH.sub.3                                                                        H   H   H   CCl          O                           CH.sub.3     CH.sub.2 COOCH.sub.3                                                                        H   H   H   CF           O                           CH.sub.3     CH.sub.2 COOCH.sub.3                                                                        H   H   H   CCl          O                           CH.sub.3                                                                                     ##STR112##  H   H   H   CF           O                           CH.sub.3                                                                                     ##STR113##  H   H   H   CCl          O                           CH.sub.3     CH.sub.2 CH.sub.2 COOCH.sub.3                                                               H   H   H   CF           O                           CH.sub.3     CH.sub.2 CH.sub.2 COOCH.sub.3                                                               H   H   H   CCl          O                            ##STR114##                                                                                  ##STR115##  H   H   H   CCl          O                            ##STR116##                                                                                  ##STR117##  H   H   H   CCl          O                            ##STR118##                                                                                  ##STR119##  H   H   H   CF           O                            ##STR120##                                                                                  ##STR121##  H   H   H   CCl          O                           CH.sub.2 CN  CH.sub.2 CN  H   H   H   CF           O                           CH.sub.2 CN  CH.sub.2 CN  H   H   H   CCl          O                           CH.sub.2 CH.sub.2 CN                                                                        CH.sub.2 CH.sub.2 CN                                                                        H   H   H   CF           O                           CH.sub.2 CH.sub.2 CN                                                                        CH.sub.2 CH.sub.2 CN                                                                        H   H   H   CCl          O                           CH.sub.3     CH.sub.2 CH.sub.2 CN                                                                        H   H   H   CF           O                           CH.sub.3     CH.sub.2 CH.sub.2 CN                                                                        H   H   H   CCl          O                           CH.sub.2 CONH.sub.2                                                                         CH.sub.2 CONH.sub.2                                                                         H   H   H   CF           O                           CH.sub.2 CONH.sub.2                                                                         CH.sub.2 CONH.sub. 2                                                                        H   H   H   CCl          O                           CH.sub.2 CON(CH.sub.3).sub.2                                                                CH.sub.2 CON(CH.sub.3).sub.2                                                                H   H   H   CF           O                           CH.sub.2 CON(CH.sub.3).sub.2                                                                CH.sub.2 CON(CH.sub.3).sub.2                                                                H   H   H   CCl          O                            ##STR122##                                                                                  ##STR123##  H   H   H   CF           O                            ##STR124##                                                                                  ##STR125##  H   H   H   CCl          O                            ##STR126##                                                                                  ##STR127##  H   H   H   CF           O                            ##STR128##                                                                                  ##STR129##  H   H   H   CCl          O                           CH.sub.3     CH.sub.2 CH.sub.2 CONH.sub.2                                                                H   H   H   CF           O                           CH.sub.3     CH.sub.2 CH.sub.2 CONH.sub.2                                                                H   H   H   CCl          O                           CH.sub.2 CH.sub.2 SCH.sub.3                                                                 CH.sub.2 CH.sub.2 SCH.sub.3                                                                 H   H   H   CF           O                           CH.sub.2 CH.sub.2 SCH.sub.3                                                                 CH.sub.2 CH.sub.2 SCH.sub.3                                                                 H   H   H   CCl          O                           CH.sub.2 CH.sub.2 SOCH.sub.3                                                                CH.sub.2 CH.sub.2 SOCH.sub.3                                                                H   H   H   CF           O                           CH.sub.2 CH.sub.2 SOCH.sub.3                                                                CH.sub.2 CH.sub.2 SOCH.sub.3                                                                H   H   H   CCl          O                           CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                         CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                         H   H   H   CF           O                           CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                         CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                         H   H   H   CCl          O                           H            cyclohexyl   H   H   H   CH           O                           H            cyclohexyl   H   H   H   N            O                           H            cyclohexyl   H   H   H   CF           O                           H            cyclohexyl   H   H   H   CCl          O                           H            cyclohexyl   H   H   H   CCF.sub.3    O                                         ##STR130##  H   H   H   CCl          O                           H                                                                                            ##STR131##  H   H   H   CCl          O                           H                                                                                            ##STR132##  H   H   H   CCl          O                           CH.sub.3                                                                                     ##STR133##  H   H   H   CCl          O                           CH.sub.3                                                                                     ##STR134##  H   H   H   CCl          O                           CH.sub.3                                                                                     ##STR135##  H   H   H   CCl          O                            ##STR136##                                                                                  ##STR137##  H   H   H   CCl          O                            ##STR138##                                                                                  ##STR139##  H   H   H   CH           O                            ##STR140##                                                                                  ##STR141##  H   H   H   N            O                            ##STR142##                                                                                  ##STR143##  H   H   H   CF           O                            ##STR144##                                                                                  ##STR145##  H   H   H   CCl          O                            ##STR146##                                                                                  ##STR147##  H   H   H   CCF.sub.3    O                            ##STR148##               H   H   H   CF           O                            ##STR149##               H   H   H   CCl          O                            ##STR150##               H   H   H   CH           O                            ##STR151##               H   H   H   N            O                            ##STR152##               H   H   H   CF           O                            ##STR153##               H   H   H   CCl          O                            ##STR154##               H   H   H   CCF.sub.3    O                            ##STR155##               H   H   H   CF           O                            ##STR156##               H   H   H   CCl          O                            ##STR157##               H   H   H   CH           O                            ##STR158##               H   H   H   N            O                            ##STR159##               H   H   H   CF           O                            ##STR160##               H   H   H   CCl          O                            ##STR161##               H   H   H   CF           O                            ##STR162##               H   H   H   CCl          O                            ##STR163##               H   H   H   CCF.sub. 3   O                            ##STR164##               H   H   H   CCl          O                            ##STR165##               H   H   H   CCl          O                           CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                                      H   H   H   CF           O                           CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                                      H   H   H   CCl          O                            ##STR166##               H   H   H   CCl          O                           CH.sub.3     C.sub.2 H.sub.5                                                                             H   H   H   CH           O                           CH.sub.3     C.sub.2 H.sub.5                                                                             H   H   H   N            O                           CH.sub.3     C.sub.2 H.sub.5                                                                             H   H   H   CCF.sub.3    O                           C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   CH           O                           C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   N            O                           C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H   H   H   CCF.sub.3    O                           C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   CH           O                           C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   N            O                           C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         H   H   H   CCF.sub.3    O                           CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                                      H   H   H   CH           O                           CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                                      H   H   H   N            O                            ##STR167##               H   H   H   CH           O                            ##STR168##               H   H   H   N            O                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                      H   H   H   CH           O                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                      H   H   H   N            O                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                      H   H   H   CCF.sub.3    O                            ##STR169##               H   H   H   CF           O                            ##STR170##               H   H   H   CCl          O                            ##STR171##               H   H   H   CF           O                            ##STR172##               H   H   H   CCl          O                            ##STR173##               H   H   H   CF           O                            ##STR174##               H   H   H   CCl          O                            ##STR175##               H   H   H   CF           O                            ##STR176##               H   H   H   CCl          O                            ##STR177##               H   H   H   CF           O                            ##STR178##               H   H   H   CCl          O                           CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                             H   H   H   CCl          O                           __________________________________________________________________________

The present compound (I) has an excellent herbicidal activity and some of them have excellent selectivity between crops and weeds.

That is, the present compound, when used for foliar treatment and soil treatment in upland fields, exhibits a herbicidal activity against various weeds in question. Also, the present compound (I), when used for flooding treatment is paddy fields, exhibits a herbicidal activity against various weeds in question.

The present compound (I) can control a wide range of weeds generated in crop lands or non-crop lands, can be applied in low dosage rates, has a broad herbicidal spectrum and also can safely be used for no-till cultivation in soybean fields, peanut fields, corn fields, etc.

As weeds which can be controlled by the present compound, there are mentioned for example broad-leaved weeds such as wild buckwheat (Polygonum convolvulus), pale smartweed (Polygonum lapathifolium), common purslane (Portulaca oleracea), chickweed (Stellaria media), common lambsquarters (Chenopodium album), redroot pigweed (Amaranthus retroflexus), radish (Raphanus sativus), wild mustard (Sinapis arvensis), shepherds purse (Capsella bursa-pastoris), hemp sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), velvetleaf (Abutilon theophrasti), prickly sida (Sida spinosa), field pansy (Viola arvensis), cleavers (Galium aparine), ivyleaf morningglory (Ipomoea hederacea), tall morningglory (Ipomoea purpurea), field bindweed (Convolvulus arvensis), red deadnettle (Lamium purpureum), henbit (Lamium amplexicaure), jimsonweed (Datura stramonium), black nightshade (Solanium nigrum), birdseye speedwell (Veronica persica), cocklebur (Xanthium strumarium), sunflower, (Helianthus annuus), scentless chamomile (Matricaria perforata), corn marigold (Chrysanthemum segetum), etc.; Gramineae weeds such as Japanese millet (Echinochloa frumentacea), barnyardgrass (Echinochloa crus-galli) green foxtail (Setaria viridis) large carbgrass (Digitaria sanguinalis), annual bluegrass (Poa annua), blackgrass (Alopecurus myosuroides), oat (Avena sativa), wild oat (Avena fatua), johnsongrass (Sorghum halepense), quackgrass (Agropyron repens), downy brome (Bromus tectorum), bermudagrass (Cynodon dactylon), etc.; Commelinaceae weeds such as dayflower (Commelina communis), etc.; and Cyperacease weeds such as rice flatsedge (Cyperus iria), purple nutsedge (Cyperus rotundus), etc. In addition, the present compounds give such no phytotoxicity as becoming a problem to main crops such as corn, wheat, barley, rice, soybean, cotton, beet, etc.

In following treatment in paddy fields, the present compounds exhibit a herbicidal activity against gramineous weeds such as barnyardgrass (Echinochloa oryzicola), etc.; broad-leaved weeds such as false pimpernel (Lindernia procumubens), indian toothcup (Rotala indica), waterwort (Elatine triandra), Ammannia multiflora, etc., Cyperacease weeds such as smallflower umbrellaplant (Cyperus difformis), bulrush (Scirpus juncoides), slender spikerush (Elecoharis acicularis), water nutgrass (Cyperus serotinus), etc.; monochloria (Monochoria vaginalis), arrowhead (Sagittaria pygmaea), etc.

When the present compound (I) is used as an active ingredient for herbicides, it is usually formulated before use into emulsifiable concentrates, wettable powders, suspension formulations, granules, water-dispersible granules, etc. by mixing with solid carriers, liquid carriers, surface active agents or other auxiliaries for formulation.

The content of the compound (I) as an active ingredient in these preparations is normally within a range of about 0.001 to 90% by weight, preferably of about 0.003 to 80% by weight.

Examples of the solid carriers are fine powders or granules of kaolin clay, attapulgite clay, bentonite, terra abla, pyrophyllite, talc, diatomaceous earth, calcite, walnut shell powders, urea, ammonium sulfate and synthetic hydrated silicon dioxide, etc.

Examples of the liquid carriers are aromatic hydrocarbons (e.g. xylene, methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol, cellosolve), ketones (e.g. acetone, cyclohexanone, isophorone), vegetable oil [soybean oil, cotton seed oil), dimethyl sulfoxide, N,N-dimethylformamide, acetonitrilo water, etc.

Examples of the surface active agents used for emulsification, dispersion or spreading, etc. are anionic surface active agents such as salts of alkyl sulfates, alkylsulfonates, alkylarylsulfonates, dialkyl sulfosuccinates, salts of polyoxyethylene alkylaryl ether phosphoric acid esters, etc., and nonionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc.

Examples of other auxiliaries for formulation are lignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.

The present compound (I) is usually formulated and used in soil treatment, foliar treatment or flooding treatment before or after emergence of weeds. The soil treatment includes soil surface treatment, soil incorporation treatment, etc. The foliar treatment includes, in addition to treatment of plants from above, directed treatment in which treatment is limited to weeds only so as not to adhere to crops.

Build-up of the herbicidal activity of the present compound (I) can be expected by using them in mixture with other herbicides. Further, the present compound (I) can also be used in mixture with insecticides, acaricides, nematocides, fungicides, plant growth regulators, fertilizers, soil improvers, etc.

The present compound(I) can be used as an active ingredient for herbicides used in paddy fields, ridges of paddy fields, plowed fields, non-plowed fields, orchards, pastures, turfs, forests and non-agricultural fields, etc.

When the present compound (I) is used as an active ingredient for herbicides, their dosage rate varies with weather conditions, preparation forms, when, how and where the treatment is carried out, weeds species to be controlled, crops species to be protected, etc. Usually, however, the dosage rate is from 0.003 grams to 100 grams of the active ingredient per are, preferably from 0.01 grams to 50 grams of active gredient per are.

The herbicidal composition of the invention formulated in the form of an emulsifiable concentrate, a wettable powder or a suspension formulations may ordinarily be employed by diluting it with water at a volume of about 1 to 10 liters per are (if necessary, auxiliaries such as a spreading agent are added to the water). The granules are usually applied as they are without being diluted.

The spreading agent includes, in addition to the foregoing surface active agents, substances such as polyoxyethylene resin acids (esters), lignosulfonates, abietates, dinaphthylmethanedisulfonates, paraffin, etc.

The present invention will be illustrated in more detail with reference to the following production examples, formulation examples and test examples, which are not however to be interpreted as limiting the invention thereto.

First, production examples for the present compound (I) are shown.

PRODUCTION EXAMPLE 1

0.55 Gram of 2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoic acid was dissolved in 3 ml of dry tetrahydrofuran, and 0.35 g of N,N'-carbonyliimidazole was added. After stirring at room temperature for 20 minutes, a methylene chloride solution of N,N-dimethylhydroxylamine prepared from 0.39 g of N,N-dimethylhydroxylamine hydrochloride and 0.44 g of triethylamine was added, and stirring was carried out at room temperature for 12 hours. The reaction mixture was poured into a 1N hydrochloric acid, and the resulting mixed solution was extracted with ethyl acetate. The organic layer was separated, washed twice with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to column chromatography on silica gel to obtain 0.50 g of 4,6-dimethoxy-2-{(2-(N,N-dimethylaminooxycarbonyl)phenoxy}pyrimidine [present compound (1)].

Melting point: 71.0°˜72.5° C.

¹ H-NMR (CDCl₃) δ: 2.62 (s, 6H) 3.75 (s, 6H) 5.70 (s, 1H), 6.09-8.01 (m, 4H)

IR (nujol): 1750, 1614 cm⁻¹

PRODUCTION EXAMPLE 2

0.55 Gram of 2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoic acid was dissolved in 5 ml of dry tetrahydrofuran, and 0.35 g of N,N'-carbonyldiimidazole was added. After stirring at room temperature for 20 minutes, 0.20 g of N-hydroxypiperidine was added, and stirring was carried out at room temperature for 12 hours. The reaction mixture was poured into a 1N hydrochloric acid, and the resulting mixed solution was extracted with ethyl acetate. The organic layer was separated, washed twice with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to column chromatography on silica gel to obtain 0.54 g of 4,6-dimethoxy-2-{2-(1-piperidyloxycarbonyl)phenoxy}pyrimidine [present compound (2)].

n_(D) ²².7 : 1.5454

¹ H-NMR (CDCl₃) δ: 1.0-3.5 (m, 10H), 3.74 (s, 6H) 5.69 (s, 1H), 7.07-8.00 (m, 4H)

IR (neat): 2952, 1748, 1604 cm⁻¹

PRODUCTION EXAMPLE 3

0.55 Gram of 2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoic acid was dissolved in 3 ml of dry tetrahydrofuran. To the resulting solution was added a methylene chloride solution of N-tert-butylhydroxylamine prepared from 0.50 g of N-tert-butylhydroxylamine hydrochloride and 0.44 g of triethylamine. Subsequently, 0.85 g of 2,4,6-triisopropylbenzenesulfonyl chloride and 0.45 g of 1-methylimidazole were added, and the resulting mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into a 1N hydrochloric acid, and the resulting mixed solution was extracted with ethyl acetate. The organic layer was separated, washed twice with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to column chromatography on silica gel to obtain 0.30 g of 2-{2-(N-tert-butylaminooxycarbonyl)phenoxy}-4,6-dimethoxypyrimidine [present compound (3)].

n_(D) ²⁵ : 1.5351

¹ H-NMR (CDCl₃) δ: 1.10 (s, 9H) 3.73 (s, 6H), 5.69 (s, 1H), 6.45 (bs, 1H), 7.10-8.04 (m, 4H)

IR (neat): 3240, 2980, 1716, 1602 cm⁻¹

PRODUCTION EXAMPLE 4

0.17 Gram of a 60% sodium hydride in oil was suspended in 4 ml of N,N-dimethylformamide, and a solution of 0.70 g of 3-hydroxy-2-(N,N-dimethylaminooxycarbonyl)pyridine in 1 ml of N,N-dimethylformamide was added. After stirring at room temperature for 30 minutes, a solution of 0.84 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine in 1 ml of N,N-dimethylformamide was added. After stirring at room temperature for 3 hours, the reaction solution was heated to 70° to 80° C. and kept at the same temperature for 2 hours with stirring. The reaction solution was allowed to cool, poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to chromatography to obtain 0.30 g of 3-(4,6-dimethoxypyrimidin-2-yl)oxy-2-(N,N-dimethylaminooxycarbonyl)pyridine [present compound (4)].

¹ H-NMR (CDCl₃) δ: 2.72 (s, 6H), 3.78 (s, 6H), 5.76 (s, 1H), 7.55-7.63 (m, 2H), 8.61 (d×d, 1H, J=4.8, 2.4 Hz)

PRODUCTION EXAMPLE 5

0.93 Gram of 2-chloro-6-(4,6-dimethoxypyrimidin-2-yl)oxybenzoic acid was dissolved in 10 ml of tetrahydrofuran, and 0.58 g of N,N'-carbonyldiimidazole was added. After stirring at room temperature for 10 minutes, the solution was refluxed for 20 minutes. After the solution was allowed to cool, 0.35 g of N,N-dimethylhydroxylamine hydrochloride and 0.36 g of triethylamine were added, and the resulting mixed solution was stirred overnight at room temperature. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was separated, washed twice with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to chromatography on silica gel to obtain 0.2 g of 4,6-dimethoxy-2-{3-chloro-2-(N,N-dimethylaminooxycarbonyl)phenoxy}pyrimidine [present compound (12)].

m.p. 80.0°-81.0° C.

¹ H-NMR (CDCl₃) δ: 2.73 (s, 6H), 3.77 (s, 6H), 5.72 (s, 1H), 7.00-7.49 (m, 3H)

PRODUCTION EXAMPLE 6

1.98 Grams of 2-fluoro-6-(4,6-dimethoxypyrimidin-2-yl)oxybenzoic acid was dissolved in 20 ml of tetrahydrofuran, and 1.31 g of N,N-carbonyldiimidazole was added. After stirring at room temperature for 20 minutes, 0.80 g of N,N-dimethylhydroxylamine hydrochloride and 0.83 g of triethylamine were added, and the resulting mixed solution was stirred at room temperature for 6 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was separated, washed twice with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to chromatography on silica gel to obtain 1.10 g of 4,6-dimethoxy-2-{3-fluoro-2-(N,N-dimethylaminooxycarbonyl)phenoxy}pyrimidine [present compound (13)].

¹ H-NMR (CDCl₃) δ: 2.68 (s, 6H), 3.77 (s, 6H), 5.72 (s, 1H), 6.82-7.62 (m, 3H)

The present compounds thus obtained are collectively shown in Table 3.

                                      TABLE 3                                      __________________________________________________________________________      ##STR179##                                                                    Com-                                             Physical properties                                                            (m.p.,                        pound                                            refractive index,             No. R.sup.1 R.sup.2 Y.sup.1                                                                            Y.sup.2                                                                            Y.sup.3                                                                            X Z     R.sup.3                                                                            R.sup.4                                                                             .sup.1 H-NMR(CDCl.sub.3,                                                       δ)                      __________________________________________________________________________     (1) CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           m.p. 71.0°                                                              C.˜72.5°                                                          C.                            (2) (CH.sub.2 ) .sub.5                                                                             H   H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.22.7 1.5454       (3) H       tert-C.sub.4 H.sub.9                                                                   H   H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.25 1.5351         (4) CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O N     OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.25 1.5440         (5) CH.sub.3                                                                               CH.sub.3                                                                               H   CH.sub.3                                                                           H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5375         (6) CH.sub.3                                                                               CH.sub.3                                                                               H   Cl  H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5418         (7) CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CH    CH.sub.3                                                                           CH.sub.3                                                                            2.32(S, 6H), 2.55(S,                                                           6H),                                                                           6.65(S, 1H),                                                                   7.08-8.00(m, 4H)              (8) CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CH    OCH.sub.3                                                                          Cl   n.sub.D.sup.25 1.5420         (9) CH.sub.3                                                                               CH.sub.3                                                                               H   H   Cl  O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.22 1.5415         (10)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   F   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.22 1.5231         (11)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   OCH.sub.3                                                                          O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.22 1.5342         (12)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           m.p. 80.0-81.0°                                                         C.                            (13)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CF    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.23 1.5271         (14)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CF    OCH.sub.3                                                                          Cl   m.p. 100.0-102.0°                                                       C.                            (15)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   S CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5672         (16)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               Cl  H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5378         (17)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               CH.sub.3                                                                           H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5403         (18)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   CH.sub.3                                                                           O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5315         (19)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   OCH.sub.3                                                                          H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5513         (20)                                                                               H       tert-C.sub.4 H.sub.9                                                                   H   H   H   O CF    OCH.sub.3                                                                          OCH.sub.3                                                                           m.p. 89.0-90.0°                                                         C.                            (21)                                                                               (CH.sub.2 ) .sub.5                                                                             H   H   H   O CF    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5351         (22)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               OCH.sub.3                                                                          H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5361         (23)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CCF.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5045         (24)                                                                               CH.sub.2 C.sub.6 H.sub.5                                                               CH.sub.2 C.sub.6 H.sub.5                                                               H   H   H   O CF    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.25 1.5538         (25)                                                                               CH.sub.2 C.sub.6 H.sub.5                                                               CH.sub.2 C.sub.6 H.sub.5                                                               H   H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           m.p. 114.0-115.0°                                                       C.                            (26)                                                                               CH.sub.2 C.sub.6 H.sub.5                                                               CH.sub.2 C.sub.6 H.sub.5                                                               H   H   H   O N     OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.25 1.5678         (27)                                                                               H       C.sub.3 H.sub.7 (i)                                                                    H   H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.25 1.5454         (28)                                                                               H       CH.sub.3                                                                               H   H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.25 1.5462         (29)                                                                               H       C.sub.3 H.sub.7 (i)                                                                    H   H   H   O N     OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.25 1.5326         (30)                                                                               (CH.sub.2 ) .sub.5                                                                             H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.25 1.5328         (31)                                                                               H       tert-C.sub.4 H.sub.9                                                                   H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5375         (32)                                                                               (CH.sub.2 ) .sub.5                                                                             H   H   H   O CCF.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5411         (33)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.23 1.5378         (34)                                                                               H                                                                                       ##STR180##                                                                            H   H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5321         (35)                                                                               H                                                                                       ##STR181##                                                                            H   H   H   O N     OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5337         (36)                                                                               CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                            H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.26.5 1.5523       (37)                                                                               CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                            H   H   H   O N     OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5430         (38)                                                                               H       CH.sub.3                                                                               H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5623         (39)                                                                               H       C.sub.3 H.sub.7 (i)                                                                    H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           1.09(d, 6H, J=6.0Hz),                                                          3.35(sep, 1H,                                                                  J=6.0Hz), 3.77(s, 6H),                                                         5.72(s, 1H),                                                                   6.82-7.35(s, 3H)              (40)                                                                               H                                                                                       ##STR182##                                                                            H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5458         (41)                                                                               CH.sub.2 C.sub.6 H.sub.5                                                               CH.sub.2 C.sub.6 H.sub.5                                                               H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           m.p. 57.0-59.0°                                                         C.                            (42)                                                                               (CH.sub.2 ) .sub.5                                                                             H   H   H   O N     OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.24 1.5352         (43)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O COCH.sub.3                                                                           OCH.sub.3                                                                          OCH.sub.3                                                                           m.p 115-117° C.        (44)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CC.sub.6 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           2.37(s, 6H), 3.79(s,                                                           6H), 5.70(s1H                                                                  7.07-7.57(m, 8H)              (45)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CCOOCH.sub.3                                                                         OCH.sub.3                                                                          OCH.sub.3                                                                           2.86(s, 6H), 3.78(s,                                                           6H), 5.73(s, 1H)                                                               7.30-7.91(m, 3H)              (46)                                                                               CH.sub.3                                                                               CH.sub.3                                                                               H   H   H   O CNO.sub.2                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           2.76(s, 6H), 3.76(s,                                                           6H), 5.52(s, 1H)                                                               7.17(t, 1H, J=3.8Hz),                                                          7.92-8.19(m, 2H)              (47)                                                                               CH.sub.2 CH.sub.2 OCH.sub.3                                                            CH.sub.2 CH.sub.2 OCH.sub.3                                                            H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.23.5 1.5385       (48)                                                                                ##STR183##     H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.23.5 1.5374       (49)                                                                               CH.sub.3                                                                               CH.sub.2 C.sub.6 H.sub.5                                                               H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.23.5 1.5635       (50)                                                                               CH.sub.2 CH.sub.2 Cl                                                                   CH.sub.2 CH.sub.2 Cl                                                                   H   H   H   O CH    OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.23.5 1.5386       (51)                                                                               CH.sub.3                                                                               C.sub.2 H.sub.5                                                                        H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.23.5 1.5270       (52)                                                                               CH.sub.2 CH.sub.2 CN                                                                   CH.sub.2 CH.sub.2 CN                                                                   H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           2.63(t, 4H, J=5.0Hz),                                                          2.93(t,4H                                                                      J=5.0Hz), 3.78(s, 6H),                                                         5.71(s, 1H),                                                                   7.01-7.46(m, 3H)              (53)                                                                               (CH.sub.2).sub.4                                                                               H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub. 3                                                                          n.sub.D.sup.23.5 1.5468       (54)                                                                               CH.sub.2 COOC.sub.2 H.sub.5                                                            CH.sub.2 COOC.sub.2 H.sub.5                                                            H   H   H   O CCl   OCH.sub.3                                                                          OCH.sub.3                                                                           n.sub.D.sup.25                __________________________________________________________________________                                                      1.5332                   

Production examples for the phenol derivatives (II), a starting compound, are shown.

PRODUCTION EXAMPLE 7

6.00 Grams of acetylsalicylic acid chloride was dissolved in 70 ml of methylene chloride, and 7.37 g of N,N-dimethylhydroxylamine hydrochloride was added. Then, 9.16 of triethylamine was added dropwise thereto with stirring at room temperature. After completion of addition, stirring was carried out at room temperature for further 6 hours. The reaction mixture was washed with a 0.5N hydrochloric acid and then twice with water, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to column chromatography to obtain 3.10 g of 2-(N,N-dimethylaminooxycarbonyl)phenol.

¹ H-NMR (CDCl₃) δ: 2.90 (s, 6H), 6.68-7.81 (m, 4H), 10.65 (bs, 1H)

PRODUCTION EXAMPLE 8

7.0 Grams of 3-hydroxypicolinic acid was dissolved in 10 ml of N,N-dimethylformamide, and the resulting solution was cooled to 0° to 5° C. 5.9 Grams of thionyl chloride was then added dropwise to the solution which was then stirred at 0° to 5° C. for further 30 minutes. Thereafter, 30 ml of chloroform was added to the solution which was then stirred at 0° to 5° C. for further 15 minutes. To the resulting mixed solution was added dropwise a dichloromethane solution of N,N-dimethylhydroxylamine prepared from 7.4 g of N,N-dimethylhydroxylamine hydrochloride and 7.6 g of triethylamine. After stirring at 0° to 5° C. for 30 minutes, 7.9 g of pyridine was added, and stirring was continued at 0° to 5° C. for further 1 hour. After stirring at room temperature for 8 hours, the reaction solution was poured into water, and insoluble matters were removed by filtration on celite. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to chromatography to obtain 1.0 g of 3-hydroxy-2-(N,N-dimethylaminooxycarbonyl)pyridine.

¹ H-NMR (CDCl₃) δ: 2.97 (s, 6H), 7.31-7.36 (m, 2H), 8.20 (d×d, 1H, J=3.0, 4.0 Hz), 10.30 (bs, 1H)

PRODUCTION EXAMPLE 9

1.56 Grams of 6-fluorosalicylic acid was dissolved in 20 ml of tetrahydrofuran, and 1.94 g of N,N'-carbonyldiimidazole was added. After stirring at room temperature for 30 minutes, 1.47 g of N,N-dimethylhydroxylamine hydrochloride and 1.52 g of triethylamine were added, and the resulting mixed solution was stirred at room temperature for 7 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to column chromatography to obtain 0.6 g of 3-fluoro-2-(N,N-dimethylaminooxycarbonyl)phenol.

¹ H-NMR (CDCl₃) δ: 2.91 (s, 6H), 6.36-7.50 (m, 4H), 11.05 (s, 1H)

PRODUCTION EXAMPLE 10

1.73 Grams of 6-chlorosalicylic acid was dissolved in 20 ml of tetrahydrofuran, and 1.95 g of N,N'-carbonyldiimidazole was added. After stirring at room temperature for 30 minutes, 1.47 g of N,N-dimethylhydroxylamine hydrochloride and 1.52 g of triethylamine were added, and the resulting mixed solution was stirred at room temperature for 7 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to column chromatography to obtain 1.1 g of 3-chloro-2-(N,N-dimethylaminooxycarbonyl)phenol.

¹ H-NMR (CDCl₃) δ: 2.92 (s, 6H), 6.74-7.35 (m, 6H), 10.30 (s, 1H)

m.p.: 104°-106° C.

The phenol derivatives (II) thus obtained are collectively shown in Table 4.

                                      TABLE 4                                      __________________________________________________________________________      ##STR184##                                                                    R.sup.1                                                                             R.sup.2                                                                              Y.sup.1                                                                           Y.sup.2                                                                          Y.sup.3                                                                          Z  X Physical properties (m.p., refractive index,                                   .sup.1 H-NMR(CDCl.sub.3, δ))                      __________________________________________________________________________     CH.sub.3                                                                            CH.sub.3                                                                             H  H H CH O 2.90(s, 6H), 6.68-7.81(m, 4H), 10.65(bs, 1H)            CH.sub.3                                                                            CH.sub.3                                                                             H  H H N  O 2.97(s, 6H), 7.31-7.36(m, 2H), 8.20(d×d, 1H,                             J=3.0, 4.0Hz), 10.30(bs, 1H)                            CH.sub.3                                                                            CH.sub.3                                                                             H  H H CF O 2.91(s, 6H), 6.36-7.50(m, 4H), 11.05(s, 1H)             CH.sub.3                                                                            CH.sub.3                                                                             H  H H CCl                                                                               O m.p. 104-106° C.                                 CH.sub.3                                                                            CH.sub.3                                                                             CH.sub.3                                                                          H H CH O n.sub.D.sup.24 1.5272                                   CH.sub.2 C.sub.6 H.sub.5                                                            CH.sub.2 C.sub.6 H.sub.5                                                             H  H H CH S n.sub.D.sup.24 1.6118                                   H    C.sub.4 H.sub.9 (tert)                                                               H  H H CH O n.sub.D.sup.24 1.5148                                   H    C.sub.4 H.sub.9 (tert)                                                               H  H H CCl                                                                               O n.sub.D.sup.24 1.5019                                   CH.sub.2 C.sub.6 H.sub.5                                                            CH.sub.2 C.sub.6 H.sub.5                                                             H  H H CH O m.p 94-95° C.                                    CH.sub.2 C.sub.6 H.sub.5                                                            CH.sub.2 C.sub.6 H.sub.5                                                             H  H H CCl                                                                               O m.p 116-117° C.                                  (CH.sub.2 ) .sub.5                                                                        H  H H CH O n.sub.D.sup.24 1.5383                                   (CH.sub.2 ) .sub.5                                                                        H  H H CCl                                                                               O m.p 136-137° C.                                  __________________________________________________________________________

Formulation examples are shown below. In the examples, the present compound (I) is shown by Compound No. in Table 3, and parts are by weight.

FORMULATION EXAMPLE 1

Fifty part of the present compound (1), (12), (14), (20), (25), 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrated silicon dioxide are well mixed while being powdered to obtain a wettable powder.

FORMULATION EXAMPLE 2

Ten parts of the present compound (1)-(32), 14 parts of polyoxyethylene styrylphenl ether, 6 parts of calcium dodecylbenzenesulfonate, 40 parts of xylene and 30 parts of cyclohexanone are well mixed to obtain an emulsifiable concentrate.

FORMULATION EXAMPLE 3

Two parts of the present compound (1), (12), (14), (20), (25), 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed. The resulting mixture is well kneaded with water, granulated and dried to obtain a granule.

FORMULATION EXAMPLE 4

Twenty five parts of the present compound (1)-(32), 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed and wet-pulverized until the particle size decreases to 5 microns or less. Thus, a suspension formulation is obtained.

That the present compounds are useful as an active ingredient for herbicides is shown by test examples. In the examples, the present compound (I) is shown by Compound No. in Table 3, and compounds used for comparison are shown by Compound symbol in Table 5.

                  TABLE 5                                                          ______________________________________                                         Com-                                                                           pound                                                                          symbol                                                                               Structural formula     Remarks                                           ______________________________________                                                ##STR185##            Japanese Patent Application Kokai No.                                          63-115870. (n.sub.D.sup.23 1.5271)                B                                                                                     ##STR186##            Comparative compound (n.sub.D.sup.23                                           1.5475)                                           C                                                                                     ##STR187##            Japanese Patent Application Kokai No.                                          63-115870.                                        D                                                                                     ##STR188##            Japanese Patent Application Kokai No.                                          62-17059.                                         E                                                                                     ##STR189##            Japanese Patent Application Kokai No.                                          62-174059.                                        F                                                                                     ##STR190##            Japanese Patent Application Kokai No.                                          62-174059.                                        G                                                                                     ##STR191##            Comparative compound  (n.sub.D.sup.19                                          1.5298)                                           H                                                                                     ##STR192##            Japanese Patent Application Kokai No.                                          62-174059.                                        I                                                                                     ##STR193##            Japanese Patent Application Kokai No.                                          62-174059.                                        J                                                                                     ##STR194##            Japanese Patent Application Kokai No.                                          68-84.                                            K                                                                                     ##STR195##            Japanese Patent Application Kokai No.                                          64-84.                                            L                                                                                     ##STR196##            Japanese Patent Application Kokai No.                                          64-84.                                            M                                                                                     ##STR197##            Japanese Patent Application Kokai No.                                          1-250378.                                         ______________________________________                                    

The evaluation of the herbicidal activity and phytotoxicity was carried out as follows: When the states of emergence and growth of treated test plants (weeds and crops) at the time of evaluation were completely the same as or hardly different from those of untreated test plants, the value of evaluation was taken as "0". When the treated test plants were completely killed, or their emergence and growth were completely inhibited, the value of evaluation was taken as "5", and an interval between "0" and "5" was divided into four stages, i.e. "1", "2", "3" and "4". The evaluation was thus made in six stages.

TEST EXAMPLE 1 Soil Surface Treatment Test in Upland Field Soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and the seeds of Japanese millet, oat, tall morningglory and velvetleaf were sowed in the respective pots and covered with soil. The test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 6.

                  TABLE 6                                                          ______________________________________                                                Dosage                                                                         rate of Herbicidal activity                                                      active                  Tall                                          Test     ingredient                                                                               Japanese      morning-                                                                              Velvet-                                compound (g/a)     millet   Oat  glory  leaf                                   ______________________________________                                         (1)      5         5        5    --     5                                               1.25      5        4    --     4                                      (2)      5         5        5    4      4                                               1.25      5        4    --     4                                      (3)      5         5        5    --     5                                               1.25      5        4    --     4                                      (8)      5         4        4    --     --                                     (10)     5         5        4    --     4                                               1.25      4        4    --     4                                      (11)     5         5        4    --     --                                     (12)     5         5        5    5      5                                               1.25      5        5    4      5                                               0.31      5        4    4      5                                      (13)     5         5        5    5      5                                               1.25      5        5    4      5                                               0.31      5        5    4      5                                      (14)     5         5        4    --     4                                               1.25      4        4    --     4                                      (20)     5         5        5    4      5                                               1.25      5        5    4      5                                               0.31      5        5    --     4                                      (21)     5         5        5    4      5                                               1.25      5        5    4      4                                               0.31      5        4    --     4                                      (23)     5         5        4    4      4                                               1.25      5        --   4      4                                      (24)     5         5        4    --     4                                               1.25      5        4    --     4                                      (25)     5         5        4    --     4                                      (27)     5         5        5    4      4                                               1.25      5        4    --     4                                      (28)     5         5        4    --     4                                      (29)     5         5        4    --     4                                      (30)     5         5        4    4      4                                               1.25      5        4    4      4                                      (31)     5         5        4    4      5                                               1.25      5        4    4      5                                      (32)     5         5        4    4      5                                               1.25      5        --   4      4                                      A        5         4        3    0      1                                               1.25      2        1    --     0                                      B        5         0        0    0      0                                               1.25      0        0    --     0                                      C        5         4        3    0      2                                               1.25      2        1    --     0                                      D        5         3        3    0      1                                               1.25      1        2    --     0                                      G        5         --       3    0      --                                              1.25      2        2    0      2                                      L        5         2        2    0      3                                               1.25      1        0    0      2                                      M        5         3        2    0      3                                               1.25      0        0    0      2                                      ______________________________________                                    

TEST EXAMPLE 2 Foliar Treatment Test in Upland Field Soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and the seeds of Japanese millet, oat, radish and velvetleaf were sowed in the respective pots and cultivated for 8 days in a greenhouse.

Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with a spreading agent-containing water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined.

The results are shown in Table 7.

                  TABLE 7                                                          ______________________________________                                                Dosage                                                                         rate of                                                                        active  Herbicidal activity                                             Test     ingredient                                                                               Japanese            Velvet-                                 compound (g/a)     millet   Oat  Radish                                                                               leaf                                    ______________________________________                                         (1)      5         5        5    4     5                                       (2)      5         5        5    --    4                                       (3)      5         5        5    4     5                                       (4)      5         5        5    5     5                                                1.25      5        5    5     5                                       (10)     5         4        --   5     5                                       (11)     5         5        --   5     --                                      (12)     5         5        5    5     5                                                1.25      5        5    5     5                                       (13)     5         5        5    5     5                                                1.25      5        5    5     5                                       (20)     5         5        5    5     5                                                1.25      4        5    5     5                                       (21)     5         5        5    5     5                                                1.25      4        5    5     5                                       (23)     5         5        4    5     5                                                1.25      5        --   5     5                                       (24)     5         5        5    5     5                                                1.25      4        4    5     5                                       (25)     5         4        4    4     --                                      (26)     5         5        5    5     5                                                1.25      4        4    4     4                                       (27)     5         5        5    4     4                                                1.25      4        4    4     --                                      (28)     5         5        4    5     4                                                1.25      4        4    4     --                                      (29)     5         5        5    5     5                                                1.25      5        5    5     5                                       (30)     5         5        5    5     5                                                1.25      5        4    5     5                                       (31)     5         5        5    5     5                                                1.25      5        4    5     5                                       (32)     5         5        --   5     5                                                1.25      5        --   5     5                                       A        5         4        2    1     1                                       B        5         0        0    0     0                                       C        5         3        3    1     1                                       D        5         3        2    2     1                                       I        5         2        2    2     2                                       J        5         4        --   2     --                                               1.25      2        2    1     --                                      ______________________________________                                    

TEST EXAMPLE 3 Soil Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of barnyardgrass, johnsongrass, green foxtail, wild oat and blackgrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 8.

                  TABLE 8                                                          ______________________________________                                         Dosage rate  Herbicidal activity                                               Test  of active  Barn-                                                         com-  ingredient yard-   Johnson-                                                                              Green Wild Black-                              pound (g/a)      grass   grass  foxtail                                                                              oat  grass                               ______________________________________                                         (1)   10         5       5      5     4    5                                         2.5        4       4      4     4    5                                   (2)   10         5       5      5     4    --                                        2.5        4       4      5     4    --                                  A     10         3       4      2     3    3                                         2.5        2       3      1     1    3                                   ______________________________________                                    

TEST EXAMPLE 4 Foliar Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of cron, barnyardgrass and green foxtail were sowed in the respective vats and cultivated for 16 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The condition of growth of the weeds and crop at that time varied with the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 5 to 12 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 9. This test was carried out in a greenhouse through the whole test period.

                  TABLE 9                                                          ______________________________________                                                Dosage rate        Herbicidal                                                  of active                                                                               Phyto-    activity                                             Test     ingredient toxicity  Barnyard-                                                                              Green                                    compound (g/a)      Corn      grass   foxtail                                  ______________________________________                                         (1)      2.5        0         4       5                                                 0.63       0         4       4                                        (2)      2.5        2         4       5                                                 0.63       0         4       5                                        A        2.5        0         2       0                                                 0.63       0         1       0                                        E        2.5        4         4       0                                                 0.63       1         3       0                                        ______________________________________                                    

TEST EXAMPLE 5 Soil Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of soybean, cotton, corn, velvetleaf, black nightshade, barnyardgrass, green foxtail and johnsongrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer.

After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 10.

                                      TABLE 10                                     __________________________________________________________________________     Dosage rate                                                                    of active    Phytotoxicity                                                                            Herbicidal activity                                     Test  ingredient                                                                            Soy-      Black Velvet-                                                                             Barnyard-                                                                            Green                                                                              Johnson-                           compound                                                                             (g/a)  bean                                                                              Cotton                                                                             Corn                                                                              nightshade                                                                           leaf grass foxtail                                                                            grass                              __________________________________________________________________________     (1)   5      -- --  -- 5     5    5     5   5                                        1.25   0  0   0  5     4    4     4   4                                  (2)   5      1  --  -- 5     5    5     5   4                                        1.25   0  0   -- 4     4    4     5   4                                  (3)   5      -- --  -- 4     --   4     5   4                                        1.25   0  0   0  4     --   --    --  4                                  (5)   5      0  0   0  4     --   --    --  --                                 (10)  1.25   1  --  0  4     4    4     --  4                                  (11)  5      1  0   0  --    --   4     4   4                                  (23)  1.25   -- 1   -- 5     4    5     4   5                                        0.32   -- 0   1  5     4    4     4   4                                  A     5      2  2   0  0     0    2     1   3                                        1.25   0  2   0  0     0    1     0   2                                  B     5      0  0   0  0     0    0     0   0                                  C     5      0  0   0  0     0    3     3   3                                        1.25   0  0   0  0     0    3     0   1                                  D     5      0  0   0  0     0    1     1   0                                  L     5      0  0   0  2     2    0     1   0                                        1.25   0  0   0  1     1    0     0   0                                  __________________________________________________________________________

TEST EXAMPLE 6 Foliar Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of corn, tall morningglory, cocklebur, velvetleaf, sicklepod, black nightshade, barnyardgrass, green foxtail and johnsongrass were sowed in the respective vats and cultivated for 16 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The condition of growth of the weeds and crop at that time varied with the kind of the test plants, but the test plants were in the 0.5- to 4-leaf stage and were 5 to 30 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 11. This test was carried out in a greenhouse through the whole test period.

                                      TABLE 11                                     __________________________________________________________________________            Dosage rate                                                                    of active     Herbicidal activity                                       Test   ingredient                                                                            Phytotoxicity                                                                         Tall    Cock-                                                                              Velvet-                                                                             Sickle-                                                                            Black Barnyard-                                                                            Green                                                                              Johnson-             compound                                                                              (g/a)  Corn   morningglory                                                                           lebur                                                                              leaf pod nightshade                                                                           grass foxtail                                                                            grass                __________________________________________________________________________     (1)    1.25   0      4       4   5    4   5     4     4   5                           0.32   0      --      --  4    --  5     4     4   5                    (2)    5      --     5       4   5    4   5     4     5   5                           1.25   1      4       4   --   --  5     4     5   5                    (3)    5      --     4       4   5    4   5     5     4   5                           1.25   0      --      --  4    --  5     4     4   5                    (4)    1.25   1      4       --  5    4   5     5     5   5                           0.32   0      4       --  5    4   5     5     5   5                    (9)    5      0      4       --  5    4   5     4     4   4                           1.25   0      --      --  5    --  5     --    4   4                    (10)   1.25   1      4       4   5    4   5     4     4   4                           0.32   0      4       --  5    4   5     4     4   4                    (11)   1.25   1      4       --  5    4   5     5     4   4                           0.32   1      --      --  4    --  5     5     4   4                    A      5      1      1       0   0    1   --    2     0   2                    B      5      0      0       0   0    0   0     0     0   0                    C      5      0      1       0   3    2   3     2     1   2                    E      5      4      0       0   --   1   3     4     2   --                          1.25   2      0       0   1    0   2     2     0   3                    M      1.25   3      4       --  4    4   5     5     5   5                           0.32   1      3       --  --   2   2     3     2   3                    __________________________________________________________________________

TEST EXAMPLE 7 Soil Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of beet, wheat, barley, pale smartweed, cleavers, chickweed, birdseye speedwell, field pansy, downy brome, wild oat, blackgrass and annual bluegrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 25 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 12.

                                      TABLE 12                                     __________________________________________________________________________         Dosage rate                                                                Test                                                                               of active Herbicidal activity                                              com-                                                                               ingredient                                                                            Phytotoxicity                                                                             Pale       Chick-                                                                             Birdseye                                                                             Field                                                                              Downy                                                                              Wild                                                                              Black-                                                                             Annual               pound                                                                              (g/a)  Beet                                                                              Wheat                                                                              Barley                                                                             smartweed                                                                            Cleavers                                                                            weed                                                                               speedwell                                                                            pansy                                                                              brome                                                                              oat                                                                               grass                                                                              bluegrass            __________________________________________________________________________     (1) 2.5    -- 1   0   4     5    5   5     4   5   4  5   4                        0.63   -- 0   0   4     5    --  5     4   5   4  5   4                    (2) 2.5    -- --  --  4     4    4   5     4   5   4  4   4                        0.63   -- 0   1   --    --   --  5     4   5   -- 4   4                    (3) 2.5    -- 1   --  4     --   --  4     --  5   4  --  4                        0.63   -- 0   --  --    --   --  4     --  4   -- --  4                    (4) 2.5    0  0   0   --    --   4   --    --  4   -- --  --                   (5) 2.5    0  0   0   4     --   --  4     4   4   -- --  4                    (10)                                                                               2.5    -- --  --  4     4    5   5     5   4   4  4   4                        0.63   -- 1   1   4     --   4   5     4   --  -- 4   4                    (11)                                                                               2.5    1  --  0   4     --   --  4     4   4   4  4   4                    (14)                                                                               2.5    1  --  --  4     --   --  5     --  5   4  5   4                        0.63   0  1   1   --    --   --  4     --  4   4  4   4                    A   2.5    2  2   3   1     1    0   1     0   --  1  3   3                    B   2.5    0  0   0   0     0    0   0     0   0   0  0   0                    C   2.5    3  3   3   3     3    3   3     1   --  3  3   3                    D   2.5    2  0   2   0     0    0   2     0   --  2  2   3                    E   2.5    4  4   4   --    2    2   --    --  --  3  3   --                       0.63   4  2   4   3     2    1   3     3   3   3  3   --                   G   2.5    0  0   0   1     0    0   3     2   0   0  0   --                       0.63   0  0   0   0     0    0   0     1   0   0  0   1                    L   2.5    3  0   2   1     0    2   --    0   2   0  0   3                        0.63   0  0   0   0     0    0   --    0   0   0  0   0                    __________________________________________________________________________

TEST EXAMPLE 8 Foliar Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of wheat, pale smartweed, cleavers, chickweed, birdseye speedwell, field pansy, downy brome, wild oat, blackgrass and annual bluegrass were sowed in the respective vats and cultivated for 31 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The condition of growth of the weeds and crop at that time varied with the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 3 to 25 cm in height. Twenty-five days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 13. This test was carried out in a greenhouse through the whole test period.

                                      TABLE 13                                     __________________________________________________________________________     Dosage rate                                                                    of active           Herbicidal activity                                        Test  ingredient                                                                            Phytotoxicity                                                                         Pale             Birdseye                                                                             Field                                                                              Downy                                                                              Wild                                                                              Black-                                                                             Annual               compound                                                                             (g/a)  Wheat  smartweed                                                                            Cleavers                                                                            Chickweed                                                                            speedwell                                                                            pansy                                                                              brome                                                                              oat                                                                               grass                                                                              bluegrass            __________________________________________________________________________     (1)   2.5    --     4     4    4     4     4   4   4  4   4                          0.63   0      4     --   --    4     4   4   -- 4   4                    (2)   2.5    --     4     4    --    5     5   5   5  4   4                          0.63   1      4     --   --    4     4   4   -- 4   4                    (3)   2.5    --     4     4    --    4     4   --  -- --  4                    (4)   2.5    --     4     4    5     5     4   4   4  4   4                          0.63   --     4     --   5     4     4   4   4  4   4                    (10)  2.5    --     4     5    4     4     5   --  -- --  4                    A     2.5    2      2     --   0     3     --  3   3  2   2                          0.63   1      1     1    0     1     0   1   1  1   0                    B     2.5    0      0     0    0     0     0   0   0  0   0                    C     2.5    3      2     0    0     3     --  --  3  --  2                          0.63   2      0     0    0     0     0   3   2  3   1                    D     2.5    0      0     0    0     0     0   0   0  0   0                    F     2.5    --     2     --   2     3     --  3   3  2   2                          0.63   2      2     --   2     2     2   2   -- 2   2                    __________________________________________________________________________

TEST EXAMPLE 9 Flooding Treatment Test in Paddy Field

Cylindrical plastic pots of 8 cm in diameter and 12 cm in depth were filled with paddy field soil, and the seeds of barnyardgrass and bulrush were sowed 1 to 2 cm deep under the soil surface. After creating the state of paddy field by flooding, the tuber of arrowhead was buried 1 to 2 cm deep under the soil surface and cultivated in a greenhouse. After 6 days (at the initial stage of generation of every weed), the test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with 2,5 ml of water and applied onto the water surface. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 14.

                  TABLE 14                                                         ______________________________________                                                Dosage rate                                                                    of active                                                                               Herbicidal activity                                            Test     ingredient Barnyard-                                                  compound (g/a)      grass     Bulrush                                                                               Arrowhead                                 ______________________________________                                         (12)     0.16       4         4      4                                                  0.04       4         4      4                                         (13)     0.16       5         4      4                                                  0.04       4         4      4                                         H        0.16       3         3      3                                                  0.04       0         0      2                                         K        0.16       0         0      2                                                  0.04       0         0      1                                         ______________________________________                                    

TEST EXAMPLE 10 Soil Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of tall morningglory, velvetleaf, sicklepod, black nightshade, barnyardgrass, green foxtail and johnsongrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 15.

                                      TABLE 15                                     __________________________________________________________________________     Dosage rate  Herbicidal activity                                                     of active                                                                             Tall Black                                                        Test  ingredient                                                                            morning-                                                                            night-                                                                             Velvet-                                                                             Sickle-                                                                            Barnyard-                                                                           Green                                                                              Johnson-                               compound                                                                             (g/a)  glory                                                                               shade                                                                              leaf pod grass                                                                               foxtail                                                                            grass                                  __________________________________________________________________________     (12)  0.63   4    5   4    4   5    5   5                                            0.16   4    5   4    4   4    5   4                                      (13)  0.63   --   5   4    --  4    5   5                                            0.16   --   4   4    --  4    4   4                                      E     0.63   0    --  2    0   3    --  --                                           0.16   0    3   1    0   1    2   2                                      F     0.63   1    --  2    2   3    3   3                                            0.16   0    2   1    0   1    1   1                                      G     0.63   0    1   0    1   1    1   2                                            0.16   0    0   0    0   0    0   0                                      K     0.63   0    2   3    0   2    3   3                                            0.16   0    0   1    0   0    0   1                                      __________________________________________________________________________

TEST EXAMPLE 11 Foliar Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of tall morningglory, velvetleaf, black nightshade, barnyardgrass, green foxtail and johnsongrass were sowed in the respective vats and cultivated for 16 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The condition of growth of the weeds and crop at that time varied with the kind of the test plants, but the test plants were in the 0.5- to 4-leaf stage and were 4 to 27 cm in height. Eighteen days after application, the herbicidal activity was examined. The results are shown in Table 16. This test was carried out in a greenhouse through the whole test period.

                                      TABLE 16                                     __________________________________________________________________________     Dosage rate  Herbicidal activity                                                     of active                                                                             Tall                                                              Test  ingredient                                                                            morning-                                                                            Velvet-                                                                             Black Barnyard-                                                                            Green                                                                              Johnson-                                compound                                                                             (g/a)  glory                                                                               leaf nightshade                                                                           grass foxtail                                                                            grass                                   __________________________________________________________________________     (12)  0.32   5    5    5     4     5   5                                             0.08   4    5    5     4     4   4                                       (13)  0.32   4    5    5     4     4   5                                             0.08   --   5    4     4     --  4                                       G     0.32   3    --   --    3     1   3                                             0.08   1    2    2     1     0   1                                       K     0.32   3    --   --    --    1   --                                            0.08   1    3    2     1     0   2                                       L     0.32   3    --   2     2     --  3                                             0.08   1    2    0     0     1   0                                       __________________________________________________________________________

TEST EXAMPLE 12 Soil Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of pale smartweed, chickweed, birdseye speedwell, field pansy, wild oat, blackgrass and annual bluegrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 25 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 17.

                                      TABLE 17                                     __________________________________________________________________________     Dosage rate                                                                    of active    Herbicidal activity                                               Test  ingredient                                                                            Pale  Chick-                                                                             Birdseye                                                                             Field                                                                              Wild                                                                              Black-                                                                             Annual                                 compound                                                                             (g/a)  smartweed                                                                            weed                                                                               speedwell                                                                            pansy                                                                              oat                                                                               grass                                                                              bluegrass                              __________________________________________________________________________     (12)  0.16   4     4   5     4   4  4   4                                            0.04   4     4   4     4   -- --  --                                     (13)  0.16   4     5   4     5   4  4   4                                            0.04   4     --  4     4   4  --  4                                      F     0.16   1     0   3     1   1  2   --                                           0.04   0     0   0     0   -- --  2                                      K     0.16   2     1   --    --  2  1   0                                            0.04   0     0   --    2   -- --  0                                      __________________________________________________________________________

TEST EXAMPLE 13 Foliar Treatment Test in Upland Field Soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and the seeds of pale smartweed, cleavers, chickweed and field pansy were sowed in the respective vats and cultivated for 31 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The condition of growth of the weeds and crop at this time varied with the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 4 to 22 cm in height. Twenty-five days after application, the herbicidal activity was examined. The results are shown in Table 18. This test was carried out in a greenhouse through the whole test period.

                  TABLE 18                                                         ______________________________________                                         Dosage rate    Herbicidal activity                                                     of active  Pale                                                        Test    ingredient smart-         Chick-                                                                               Field                                  compound                                                                               (g/a)      weed    Cleavers                                                                              weed  pansy                                  ______________________________________                                         (12)    0.32       5       5      5     5                                              0.08       4       5      4     4                                      (13)    0.32       5       5      5     5                                              0.08       4       --     4     4                                      G       0.32       2       2      1     2                                              0.08       1       1      0     1                                      ______________________________________                                     

What is claimed is:
 1. A compound represented by the formula, ##STR198## wherein each of R¹ and R², which may be the same or different, represents a hydrogen atom, a C₁ -C₆ alkyl group, a C₃ -C₆ alkenyl group, a C₃ -C₆ alkynyl group, a halo C₁ -C₆ alkyl group, a C₁ -C₆ alkoxy C₁ -C₆ alkyl group, a C₃ -C₆ alkenyloxy C₁ -C₆ alkyl group, a C₃ -C₆ alkynyloxy C₁ -C₆ alkyl group, a C₁ -C₆ alkoxycarbonyl C₁ -C₆ alkyl group, a C₃ -C₆ alkenyloxycarbonyl C₁ -C₆ alkyl group, a C₃ -C₆ alkynyloxycarbonyl C₁ -C₆ alkyl group, a cyano C₁ -C₆ alkyl group, a group represented by the formula, ##STR199## (in which each of R⁵ and R⁶, which may be the same or different, represents a hydrogen atom, a C₁ -C₆ alkyl group, a C₃ -C₆ alkenyl group or a C₃ -C₆ alkynyl group, and n represents an integer of 1, 2, 3, or 4), a group represented by the formula, ##STR200## (in which n is as defined above, R⁷ represents a C₁ -C₆ alkyl group, a C₃ -C₆ alkenyl group or a C₃ -C₆ alkynyl group, and m represents an integer of 0, 1 or 2), a cyclo C₃ -C₈ alkyl group, or an optionally substituted phenyl group, an optionally substituted benzyl group, or R¹ and R², bonded together at their ends, form an optionally substituted C₄ -C₇ alkylene group or an optionally substituted C₃ -C₆ alkylene group containing a hetero atom; the hetero atom in R¹ and R² means a nitrogen atom, an oxygen atom or a sulfur atom; X represents an oxygen atom or a sulfur atom; Z represents CY⁴ ; each of Y¹, Y², Y³, which may be the same or different, represents a hydrogen atom, a halogen atom, a C₁ -C₆ alkyl group, or a C₁ -C₆ alkoxy group; and Y⁴ represents a hydrogen atom, a hydroxyl group, a mercapto group, a nitro group, a halogen atom, a C₁ -C₆ alkyl group, a C₂ -C₆ alkenyl group, a C₂ -C₆ alkynyl group, a C₁ -C₆ alkoxy group, a C₃ -C₆ alkenyloxy group, a C₃ -C₆ alkynyloxy group, a halo C₁ -C₆ alkyl group, a halo C₂ -C₆ alkenyl group, a halo C₂ -C₆ alkynyl group, a halo C₁ -C₆ alkoxy group, a halo C₃ -C₆ alkenyloxy group, a halo C₃ -C₆ alkynyloxy group, a C₁ -C₆ alkoxy C₁ -C₆ alkyl group, a C₃ -C₆ alkenyloxy C₁ -C₆ alkyl group, a C₃ -C₆ alkynyloxy C₁ -C₆ group, a cyano group, a formyl group, a carboxyl group, a C₁ -C₆ alkoxycarbonyl group, a C₃ -C₆ alkenyloxycarbonyl group, a C₃ -C₆ alkynyloxycarbonyl group; an optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted phenylthio group, an optionally substituted benzyloxy group, an optionally substituted benzylthio group, a group represented by the formula, ##STR201## (in which R⁵ and R⁶ are as defined above), a group represented by the formula, ##STR202## (in which R⁵ and R⁶ are as defined above), ##STR203## (in which R⁷ and m are as define above), a group represented by the formula, ##STR204## (in which R⁷ and X are as defined above), or a group represented by the formula, ##STR205## (in which R⁷, m and n are as defined above), each optionally substituted group in the above being substituted with a C₁ -C₆ alkyl group, a C₁ -C₆ alkoxy group, a halo C₁ -C₆ alkyl group, a C₁ -C₆ alkoxycarbonyl group or a halogen atom. 